Note: Descriptions are shown in the official language in which they were submitted.
62301-1351
MIXED SURFACTANT LAUNDRY DETERGENT
COMPOSI~ION OF IMPROVED DETERGENCY AND METI-IOD O~ USE
This invention relates to laundry detergent composi-
tions. More particularly, this invention relates to laundry
detergents with improved detergency obtained from a mixture of an
acid-terminated non-ionic surfactant with a quaternary ammonium
salt surfactant.
There have been many disclosures in the art relating
to detergency compositions containing cationic softening agents,
including the quaternary ammonium compound softening agents, some
of which may also function as cleaning or surfactant compounds,
with non--ionic surface-active compounds. As representative of
t~is art, mention can be made of U~S. Patents 4,264,457; 4,239,
659; 4,259,217; 4,222,905; 3,951,~79; 3,360,470; 3,351,483; 3,644,
203, etc. In addition, U.S. Patents 3,537,993 3,583,912; 3,983,
079; 4,203,872; and 4,264,479 specifically disclose combinations
of non-ionic surface-active agent, cationic fabric softener and
another ionic surfactant or modifier, such as zwitterionic sur-
factants, amphoteric surfactants, and the like.
U.S. Paten-t 4,222,905 to Cockrell, Jr. discloses laun-
dry detergent compostions which ~may be in liquid form and which
are formulated from certain non-ionic surfactants and certain
cationic surfactants, at a non-ionic:cationic weight ratio of
from 5:1 to about 1:1.
Non-ionic/cationic mixed surfactant detergent composi-
tions having a non-ionic:cationic weight ratio of from about 1:1
to 40:1, in which the non-ionic surfactant is limited to the
class having a hydrophilic-lipophilic balance (HLB) of ~rom about
5 to about 17, and wherein the cationic surfactant is limited to
the class of mono-higher alkyl quaternary ammonium compounds in
which -the higher alkyl has from about 20 to about
-2- 62301-1351
30 carbon a-toms, are disclosed by Murphy in U.S. Patent ~1,239,659.
On the other hand, i-t is also known, as disclosed in
the comrnonly assigned copending Canadian patent application No.
~78, 379 filed April 4, 1985, that acid-terminated nonionic
surfactants can function as viscosity control and gel inhibiting
agents for irnproving dispensibility, dispersibility and stability
of non-aqueous liquid nonionic surfactant compositions. Further-
more, it is also disclosed in this application that when added to
the wash solution the acid-terminated nonionic surfactant is
converted to an anionic surfactant. Nevertheless, the acid-
terminated nonionic surfactants are not considered to substant-
ially contribute to the overall cleaning performance, i.e.
detergency, of the nnionic surfactant composition.
There remains a need in the art to provide fur-ther
improvements in detergency of both liquid and powdery detergent
compositions so that, for example, the compositions can be
provided in more concentrated form with a consequential improve-
ment in reduction of packaging costs and the convenience to the
consumer.
It has now been discovered -that -the detergency of -the
acid-terminated nonionic surfactants are synergistically
promoted by the presence of a quaternary ammonium salt surfact-
ant. While improved cleaning performance can be obtained over
relatively wide ratios of the acid-terminated nonionic and the
quaternary ammonium salt surfactant, best cleaning performance
has been observed at approximately 1:1 molar ratios.
According to the present invention there is provided
a substantially nonaqueous liquid detergent composition com-
prising a surfactant mixture of from about 40% to about 90% by
weight of
(A) a liquid nonionic surfactant, and from about 10% to
about 60% by weight of a complex of
i'~3 .
-2~- 62301-1351
(B) an acid-modified nonionic surfactant which is an
esterifica-tion reaction product be-tween a nonionic surfac-tant
which is a poly (C2 to C3 alkoxylated) fatty alcohol haviny a
terminal hydroxyl group wi-th a polycarboxylic acid or poly-
carboxylic acid anhydride, and
(C) an ethoxylated or propoxylated quaternary ammonium
salt surfactant having the formula (I)
R2 ~
Rl--N--Rl X- ( I)
(CHl ~CI10),
wherein
R~ is an organic group containing a straight or branched
alkyl or alkenyl group optionally substituted with up to 3
phenyl or hydroxy groups, and optionally interrupted by up to
4 structures selected from the group consisting of
+~, -C--O--,--O--CO,--C--N--.--Ec .
--C--I--,--I--11-- --0-- --O--C--O --O--C--~ C--C--
and mixtures thereof, where R4 is an alkyl or hydroxyalkyl group
containing 1 to 4 carbon atoms, or a benzyl group, and which
contains from about 8 to 22 carbon atoms, and which may addition-
ally contain up to 12 ethylene oxide groups,
R2 is the group Rl or an alkyl or hydroxyalkyl group con-
taining 1 to 6 carbon atoms, or a benzyl group;
R i5 the group R or (CH2CHZO)qM,
Z is hydrogen or methyl, and q and p are, independently,
numbers from 1 to 12; and
X is a water-soluble anion, said complex comprising a molar
ratio of (B)/(C) in the range of from about 3:1 to 1;3.
i~.
~ 6230~-1351
In a more preferred embodiment, the presen-t invention
provides heavy duty laundry liquid non-ionic detergent composi~
tions wherein the detergency of the non-ionic surfactant deter-
gent compound is enhanced due to the synergistic effect between
a mixture of an acid-terminated non-ionic surfactan-t and a
cationic surfactan-t.
In addition to the heavy duty laundry liquid non-ionic
detergent compositions, the presen-t invention provides, in other
embodiments, aqueous liquid laundry detergent compositions, and
solid detergent compositions having improved detergency due to
the presence -therein of a mixture of an acid-terminated non-
ionic surfactant and a cationic surfactant.
The acid-terminated non-ionic surfactant which is one
essential component of the detergent compositionsof this inven-
tion, can be considered a non-ionic surfactant which has been
modified to convert a free hydroxyl (OH) group thereof to a
moiety having a carboxyl (COO~) group, for example, by reaction
with a polycarboxylic acid anhydride, e.g. succinic anhydride.
More specifically, the non-ionic surfactant is of the type having
an organic hydrophobic moiety and an organic hydrophilic moiety,
the latter including an hydroxyl group at its terminus in which
the terminal hydroxyl group is modified to a moiety having a car-
boxyl group. Preferably, the reaction product between the non-
ionic surfactant and the polycarboxylic acid anhydride forms the
partial, e.g. half, ester of the polycarboxylic acid.
Specific examples of the acid-terminated non-ionic sur-
factant and the manner of preparation thereof are shown below.
Example A
400 g of a non-ionic surfactant which is a C13-C15
alkanol which has been alkoxylated to introduce 6 ethylene oxide
o~r
62301-1351
and 3 propylene oxide units per alkanol unit (Plurafac RA30*) is
mixed with 32 g oE succinic anhydride and heated for 7 hours a-t
100C. The mixture is then cooled and filtered to remove unre-
acted succinic anhydride. Infrared and analysis indicates that
about one-half of the non-ionic surfactant has been converted to
the acidic half ester thereof. The resulting product, therefore,
i5 a mlxture of about equal parts of unmodified nonionic
surfactant and its acid-terminated half ester thereof and the
mixture can be used as such without separation of the unmodified
non-ionic surfactant.
Exampl _
522 g of the non-ionic surfactant sold under the trade-
mark Dobanol 25-7 (the product of ethoxylation of a C12-C15
alkanol, whieh product has about 7 ethylene oxide units per mole-
cule of alkanol) is mixed wich 100 g of succinic anhydride and
0.1 g of pyridine (which acts as an esterification catalyst) and
heated at 260C for 2 hours, cooled and filtered to remove unre-
acted succinic material. Infrared analysis indicates -that sub-
stantially all of the free hydroxyls of the surfactant have re-
acted.
Other esterification catalysts, such as, for example,alkali metal alkoxides such as sodium methoxide, may be used in
place of, or in admixture with, the pyridine.
Example C
Example B is repeated using 10~0 g of Dobanol 91-5
(the product of ethoxylation of a Cg-Cll alkanol, which product
has about 5 ethylene oxide units per molecule of alkanol) and
265 g of succinic anhydrideO
In the foregoing examples, the carboxylic acid moiety
is joined to the residue of the.non-ionie surfactant by a
*Trademark
~ 62301-1351
carboxylic ester linkage. Instead of succinic acid anhydride,
other polycarboxy]ic acid and acid anhydride compounds may be
used, for example, maleic acid, maleic anhydride, glu-taric acid,
malonic acid, ph-thalic acid, phthalic anhydride, citric acid, and
the like.
Furthermore, it is also within the scope of the present
invention to use linkages other than the carboxylic ester link-
ages, such as ether, -thioether~ or urethane linkages, formed by
conventinal reactions. For instance, to form an ether linkage,
the non-ionic surfactant may be treated with a strong base (to
convert its hydroxyl group to an ONa group, for ins-tance3 and
then reacted with a halocarboxylic acid such as chloroace-tic acid
or chloropropionic acid or the corresponding bromo compound.
Thus, the resulting carboxylic acid may have the formula R-Y-ZCOOH
where R is the residue of a non-ionic surfactant (on removal of a
terminal OH), Y is oxygen or sulfur, and Z represents an organic
linkage such as hydrocarbon group of, for example, 1 to 10 carbon
atoms, which may be attached to the oxygen (or sulfur) of the
formula directly or by means of an intervening linkage such as an
O O
oxygen-or nitrogen-containing linkage~ for example, 'C' or 'C'NH .
The nonionic syn-thetic organic detergents employed in
the practice of the invention as a precursor of the acid-terminat
ed non-ionic surfactant, or directly as non-ionic surfactant, may
be any of a wide variety of such compounds, which are well
known and, for example, are described at length in the text
Surface Active Agents, Vol. II, by Schwartz, Perry and Berch,
published in 1958 by Interscience Publishers, and in McCutcheon's
Detergents and Emulsifiers, 1969 Annual.
Usually, the nonionic detergentsare poly-lower alkoxy-
lated lipophiles wherein the desired hydrophi:Le-lipophile baLance
62301-13~1
is ob-tained from addition of a hydrophilic poly-lower alkoxy
group to a lipophilic moiety. A preferred class of the non-ionic
detergent employed is the poly-lower alkoxylated higher alkanol
wherein the alkanol is of 10 to 18 carbon atoms and wherein the
number of mols of lower alkylene oxide (of 2 or 3 carbon atoms)
is from 3 to 12. Of such materials it is preferred to employ
those wherein the hi~her alkanol is a higher fatty alcohol of 10
to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or
5 to 9 lower alkoxy groups per mol. Perferably, the lower alkoxy
is ethoxy but in some instances, it may be desirably mixed with
propoxy, the la-tter, if presen-t, usually being a minor (less than
50%) proportion. Exemplary of such compounds are those wherein
the alkanol is of 12 to 15 carbon atoms and which contain about
7 ethylene oxide groups per mol~ e.g. Neodol* 25-7 and Neodol
23-6.5, which products are made by Shell Chemical Company, Inc.
The former is a condensation product of a mixture of higher fatty
alcohols averaging abou-t 12 to 15 carbon atoms, with about 7 mols
of ethylene oxide and the latter is a corresponding mixture where-
in the carbon atom content of the higher fatty alcohol is 12 to
13 and the number of ethylene oxide groups present averages about
6.5. The higher alcohols are primary alkanols. Other examples
of such detergents include Tergitol ~ 15-S-7 and Tergitol 15-S-9,
both of which are linear secondary alcohol e-thoxylates made by
Union Carbide Corp. The former is a mixed ethoxylation product
of 11 to 15 carbon atoms linear secondary alkanol with seven mols
of ethylene oxide and the latter is a similar product but with
nine mols of ethylene oxide being reacted.
One particularly preferred group of non-ionic sur-
factants based on linear secondary alkanols are those available
from British Petroleum Co. under the designation "Surfactant T*".
*Trademark
-6-
,~
:.
~2~i5~
62301-1351
The "Surfactant T" non-ionics a.re obtained by ethoxylation of
secondary Cl~ fatty alcohols an~ have a narrow distribution of
ethylene oxide (~O) units from molecule -to molecule and have -the
following characteristics:
Cloud Point
Nonionic EO Content Pour Point (C) (1% sol'n) (C)
Surfactant T5 5 ~-2 ~25
Surfactant T7 7 -2 3~
Surfactant T8* 8 2 48
Surfactant T9 9 6 58
Surfactant T12 12 20 88
*"Surfactant T8" was artificially prepared by mixing equal amounts
of Surfactant T7 and Surfactan-t T9 (1:1 mixture)
The non-ionicsurfactant which is a linear secondary C13
fatty alcohol condensed with an average 8 moles ethylene oxide
per mole of fatty alcohol, and in which there are substantially
no molecules containing less than 7 or more than 9 moles EO, such
as less than 10~ by weight, preferably less than 3~ by weiyht, in
total, of the low and high EO substitutions, is an especially
preferred liquid non-ionic surfactant in view of its good balance
between relatively low pour point, relative high cloud point and
primarily because it is capable of resisting forming a gel when
added to cold water, for example, at temperatures as low as about
5C or lower.
Also useful in the present compositions as a componen-t
of the non-ionicdetergent are higher molecular weight non-ionics,
such as Neodol 45-11, which are similar ethylene oxide condensa--
~tion products of higher fatty alcohols, with the higher fatty
alcohol being of 14 to 15 carbon atoms and the number o-f ethylene
oxide groups per mol being about 11. Such products are also made
by Shell Chemical Company.
* Trademark
--7--
~,
~ 62301 1351
Other useful non-ionics are represen-ted by the ~lurafac
series from BASF Chemical Company which are the reaction product
of a higher linear alcohol and a mixture of ethylene and propy-
lene oxides, containing a mixed chain of e-thylene oxide and propy-
lene oxide, termianted by a hydroxyl group. Examples include
Plurafac RA30, Plurafac RA40 (a C13-C15 fatty alcohol condensed
with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac
D25 (a C13-C15 fatty alcohol condensed with 5moles propylene
oxide and 10 moles ethylene oxide) and Plurafac B26. Another
group of preferred liquid non-ionics are available from Shell
Chemical Comapny, Inc. under the Dobanol trademark: Dobanol 91-5
is an ethoxylated Cg-Cll fatty alcohol with an average of 5 moles
ethylene oxide; Dobanol 25-7 is an ethoxylated C12-C15 fatty
alcohol with an average of 7 moles ethylene oxide; etc.
In -the preferred poly-lower alkoxylated higher alkanols,
to obtain the best balance of hydrophilic and lipophilic moieties
the number of lower alkoxies will usually be from ~0% to 100% of
the number of carbon atoms in the higher alcohol, preferably 40
to 60% thereof and the non-ionic detergent will preferably con-
tain at least 50% of such preferred poly-lower alkoxy higher
alkanol. Higher molecular weight alkanols and various other
normally solid non-ionic detergents and surface active agents may
be contributory to gelation of the liquid detergent and consequen-
tly, will preferably be omitted or limited in quantity in the
compositions of the present inven-tion which are in the form of
non~aqueous liquids, although minor proportions thereof may be
employed for their cleaning properties, etc. With respect to
both preferred and less preferred non-ionic detergents, the
alkyl groups present therein are generally linear, although
branching may be tolerated, such as at a carbon next to or two
~ P
.~ 3~.
~?~
623Ul-1351
carbons removed from the terminal carbon of the straight chain
and away from the ethoxy chain, if such branched alkyl is not
more than three carbons in lenyth. Normally, the proportion of
carbon atoms in such a branchcd configuration will be minor rare-
ly exceeding 20% of the total carbon atom content of the alkyl.
Similarly, although linear alkyls which are terminally joined to
the ethylene oxide chains are highly preferred and are considered
to result in the best combination of detergency, biodegradability
and non-gelling characteristics, medial or secondary joinder to
the ethylene oxide in the chain may occur as in -the Surfactant
T non-ionicsdescribed above. When propylene oxide is present
in the lower alkylene oxide chain, it will usually be less than
20% thereof and preferably less than 10% thereof.
When greater proportions of non-terminally alkoxyla-ted
alkanols, propylene oxide-containing poly-lower alkoxylated
alkanols and less hydrophile-lipophile balanced non-ionic deter-
gents than mentioned above are employed and when other non-ionic
detergents are used instead of the preferred non-ionics recited
herein, the product resulting may.not have as good detergency,
stability, viscosity and non-gelling properties as the preferred
non-aqueous liquid compositions`but use of viscosity and gel
controlling compounds can also improve the properties of the
detergents based on such non-ionics. In some cases, as when a
higher molecular weight poly-lower alkoxylated higher alkanol is
employed, often for its detergency, the proportion thereof will
be regulated or limited as in accordance with the results of
various experiments, to obtain the desired detergency and still
have the product non-gelling and of desired viscosity. Also, it
has been found that it is only rarely necessary to utilize the
higher molecular weight non-ionics for their detergent properties
62301-1351
since -the pre~erred non-ionics described herein are excellent
detergents and additionally, permit -the attainment of the desired
viscosity in -the liquid deteryent without gelation at low -tempera-
ture. Of course, there will be broader latitude in the selection
of the non-ionicsurfactant for the aqueous and solid detergent
compositions of this invention. Mixtures of two or more of these
liquid non-ionicscan also be used and in some cases advantages
can be obtained by the use of such mixtures.
The acid-terminated-non-ionicsurfactant is used as i-ts
admixture with a cationic surfactanb to provide synergistic levels
of detergency. Substantially any cationic substance having sur-
face-active properties can be used in conjunction with the acid-
terminated non-ionicsurfactant. A particularly preferred class
of the cationic surfactant is the ethoxylated quaternary ammonium
salt surfactant compounds which are mono-, or poly-ethoxylated
with up to about 12 ethylene oxide groups, attached at one or
two of the Eour available positions on the quaternary nitrogen
atom.
More generally, however, any of the cationic surfactant
compounds disclosed in the aforementioned U.S. Patent 4,259,217
to Murphy, et al in columns 8 -to 15, inclusive, can also be used
in the composition of -this invention.
The cationic surfactants referred to above have the
general formula
- R3 - ~
R - N R X
(CH2CHO)pH
z
--10--
J~
62301-1351
wherein
R is an organic group containing a straigh-t or branched
a:Lkyl or alkenyl group optionallv substi-tu-ted with up to 3 phenyl
or hydroxy groups, and optionally interrup-ted by up to 4 struc~
tures selected from the group consisting of t ~ t ,
O O O R4 R40 H H O O O H
.. .. . - . . .. ... . . - - -
-C-O-, -O~CO, -C-N-, -N-C-, -C-N-, -N-C-, -O-, -O-C-O, -O-C-N-,
H O
-N-C-O-, and mixtures therof, where R4 is an alkyl or hydroxy-
alkyl group containing 1 to 4 car~on atoms, or a benzyl group,
and which conta~.ns from about 8 to 22 carbon atoms, and which may
additionally contain up to 12 ethylene oxide groups, R is the
group Rl or an alkyl or hydroxyalkyl group containing 1 to 6
carbon atoms, or a benzyl group; R3 is the group R2 or (CH2CHZO)-
qH; Z is hydrogen or methyl, and q and p are, independently,
numbers from 1 to 12; and X is a water-soluble anion, such as
halide, methyl sulfate, sul:Eate, nitrate, etc.
Preferably, in the above formula, Rl is an alkyl or
alkenyl group having from about 10 to 20 carbon atoms which may
optionally be substituted by an hydroxyl group, and which may
additionally contain up to 12 ethylene oxide groups; R2.is the
group Rl or an alkyl or hydroxyalkyl group containing 1 to 4 car-
bon atoms, or a benzyl group; R3 is the group R2 or (C~H40)qH;
Z is a hydrogen atom; and q and p are, independently, numbers
from 1 to 1~.
Example.s of the cationic e-thoxylated quaternary ammonium
surfactant compounds include, dipolyethoxy lauryl hydroxy ethyl
ammonium chloride, dipolyethoxy stearyl methyl ammoniumchloride,
polyethoxy distearyl methyl ammonium chloride, N-polyethoxy N-
polyethoxylated C16 alkyl N, N-dimethyl ammonium chloride,
62301-1351
dipolyethoxy palmitylalkyl methyl ammonium rne-thosulfate, etc.
Specific examples oE this class of ca-tionic surfac-
tant include N-ethyl N-cocoammonium ethoxylate (15) bisulfate
(Quaternium 54) wherein the total amount oE ethoxylation
averages 15 moles o-f ethylene oxide per mole of quaternary
nitrogen, N-methyJ-N-oleylammonium ethoxylate(2) wherein there
are an average of 2 moles of ethylene oxide per mole o-f quater-
nary nitrogen, N-methyl-N-stearylammonium propoxylate(l5) bi-
sulfate, wherein there are an average of 15 moles of propylene
oxide per quaternary nitrogen, and the like.
In the pre-ferred embodiment of the invention, the
acid-termina-ted non-ionic surfactant and the cationic surfac-
tant are combined in substantially a 1:1 molar complex. How-
ever, molar excesses of either component can also be used, for
example, molar ratios of acid-terminated non-ionic to cationic
may broadly fall within tlle range of from about ~:1 to 1:4,
preferably 1.5:1 to 1:1.5.
While the mixture of the acid-terminated non-ionic
surfactant and cationic sur-factant provide enhancecl cletergency
when used alone, it is preferred to use the surfactant mixture
in combination with at least one other surfactant. In the
preferred liquid detergent compositions, the other surfactant
is preferably one of the liquid non-ionie surfactants described
above, for example the Surfactant T8 (whe-ther prepared direc-tly
as such or as a mixture of Surfac-tant T7 and Surfactant T9),
used alone or in combination with a minor amount of an anionic,
cationic, amphoteric for zwitterionic surfactant~ These other
types of ionic and amphoteric surEactants are very well known
in the art and any of these known surfactants can be used.
3~ Aeeordingly, the highly preferred compositions of
this invention are surfactant mixtures of
- 12 -
62301~1351
(A) a liquid non-ionic surfac-tan-t,
(B) a non-ionic sur~actan-t haviny an oryanlc hydrophobic
moiety and an organic hydrophilic moiety, said hydrophilic
moiety including an hydroxyl group at its terminus, which has
been modified to convert said terminal hydroxyl group to a
moiety having a carboxyl group, (i.e. an acid-terminated non-
ionic surfactant), and
(C) a cationic surfactant, preferably an ethoxylated
quaternary ammonium salt surfactant.
The amount of the component (A) is generally in the
range of from about 40% to about 90%, preferably from about 50%
to about 80%, based on the surfactant mix-ture, and the total
amount of components (B) plus (C) is correspondingly, from about
10% to about 60%, preferably from about 20% to about 50% of the
surfactant mixture. Furthermore, up to about 20%, preferably
up to about 10%, especially preferably up to about 5% of the
liquid non-ionic surfactant may be replaced by another, e.g.
an anionic, surfactant, such as, for example, linear alkyl benzene
sulfonate, paraffin sulfonate, olefin sulfonate, alcohol sulfate,
etc.
In addition to the surfactant mixture of (A), ~B) and
(C), the invention detergent composition may also and preferably
does include water-soluble detergent builder salts. Typical
suitable builders include, for example, those disclosed in U.S.
Patents 4,316,~12; 4,264,466; and 3,630,929. Water-soluble in-
organic alkaline builder salts which can be used alone with -the
detergent compound or in admixture with other builders are
alkali metal carbonate, borates, phosphates, polyphosphates,
bicarbonates, and silicates. (Ammonium or substitu-ted ammonium
salts can also be used.) Specific examples of such salts are
-13-
62301-1351
sodium tripolyphospha-te, sodium carbonate, sodium tetraborate,
sodium pyrophosphate, potassium pyrophospha-te, sodium bicarbonate,
potassium tripolyphosphate, sodium hexame-taphosphate, sodium ses-
quicarbonate, sodium mono and diorthophosphate, and potassium
bicarbona-te. Sodium tripolyphosphate (TPP) is especially preferred.
The alkali metal silicates are useful builder salts which also
function to make the composition anticorrosive -to washing machine
parts. Sodium silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2
especially about 1/2 to 1/2.8 are preferred. Potassium silicates
of the same ratios can also be used.
Another class of builders useful herein are the water-
insoluble aluminosilicates, both of the crystalline and amorphous
type. Various crystalline zeolites (i.e. alumino-silicate are
described in British Patent 1,504,168; U.S. Patent 4,409~136 and
Canadian Patents 1,072,835 and 1,087,477. An example of amorphous
zeolites useful herein can be found in Belgium Patent 835,351.
The zeolites generally have the formula
( 2)X (A123)y (si2)Z WH2
wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from
1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9,
preferably 2.5 to 6 and M is preferably sodium. A typical zeolite
is type A or similar structure, with type 4A particularly pre-
ferred. The preferred aluminosilicates have calcium ion exchange
capacities of about 200 mi]liequivalents per gram or greater, e.g.
400 meq/g.
Other materials such as clays, particularly of the water-
insoluble types, may be useful adjuncts in compositions of this
invention. Particularly useful in bentonite. This material is
primarily montmorillonite which is-a hydrated aluminum silicate
in which about 1/6-th of the aluminum atoms may be replaced by
-14~
~ 62301-1351
magnesium atoms and with which varying amounts oE hydrogen,
sodium, po-tassium, calcium, e-tc., may be loosely combined.
The bentonite in its more purified :Eorm (i.e. free Erom any gri-t,
sand, etc.) suitable for detergents invariably contains at least
50% montmorillonite and thus its ca-tion exchange capacity is a-t
least about 50 to 75 meq. per 100 g. of bentonite. Particularly
preferred bentonite are -the Wyoming or Western U.S. bentonites
which have been sold as Thixo-Jels 1, 2, 3 and 4 by Georgia
Kaolin Co. These bentonites are known to soften textiles as
described in British Pa-tent 401,413 to Marriott and British
Patent 461,221 to Marriott and Dugan.
Examples of organic alkaline sequestrant builder salts
which can be used alone with -the detergent or in admixture with
other organic and inorganic builders are alkali metal, ammonium
or substituted ammonium, aminopolycarboxylates, e.g. sodium and
potassium ethylene diaminetetraacetate (EDTA), sodium and potass-
ium nitrilotriacetates (NTA) and triethanolammonium N-(2-hydroxy-
ethyl)nitrilodiacetates. Mixed salts of these polycarboxylates
are also suitable.
Other suitable builders of the organic type include
carboxymethylsuccinates, tartronates and glycollates. Of special
value are the polyacetal carboxylates. The polyace-tal carboxy-
lates and their use in detergent compositions are described in
4,144,226; 4,315,092 and 4,146,495. Other patents on similar
bui]ders include 4,141,676; 4,169,934; 4,201,858; 4,204,852;
4,224,420; 4,22~,685; 4,226,960; 4,233,422; 4,233,423; ~,302,564
and 4,303,777. Also relevant are European Pa-ten-t Application Nos.
0015024; 0021491 and 0063399.
Since the compositions of this inven-tion are generally
highly concentrated, and, therefore, may be used at rela-tively
.~ ,
~ 6230~1351
low dosages, it is desirable to supplement any phosphate builder
(such as sodium tripolyphosphate) with an auxiliary builder such
as a polymeric carboxylic acid having high calcium binding
capacity -to inhibit incrustation which could otherwise be caused
by formation of an insoluble calcium phosphate. Such auxiliary
builders are also well known in the art.
Various other detergent additives or adjuvants may be
present in the detergent product to give it additional desired
properties, either of functional or aesthetic nature~ Thus, there
may be included in the formulation, minor amounts of soil
suspending or anti-redeposition agents, e.g. polyvinyl alcohol,
fatty amides, sodium carboxymethyl cellulose, hydroxy-prop methyl
cellulose; optical brighteners, e.g. cotton, amine and polyes-ter
brighteners, for example, stilbene, tria~ole and benzidine
sulfone ~ompositions, especially sulfonated substituted triazinyl
stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone,
etc., most preferred are stilbene and triazole combinations.
Bluing agents such as ultramarine blue; enzymes, pre-
ferably proteolytic enzymes, such as subtilisin, bromelin, papin,
trypsin and pepsin, as well as amylase type enzymes, lipase type
enzymes, and mix-~ures thereof; ~actericides, e.g. tetrachloro-
salicylanilide, hexachlorophene; fungicides; dyes; pigments
(water dispersible); preservatives; ultraviolet absorbers; anti-
yellowing agents, such as sodium carboxymethyl cellulose, com-
plex of C12 to C22 alkyl alcohol with C12 to C18 alkylsulfate;
pH modifiers and pH buffers; color safe bleaches, perfume, and
anti-foam agents or suds-suppressors, e.g. silicon compounds can
also be used.
The bleaching agents are classified broadly, for con-
venience, as chlorine bleaches and oxygen bleaches. Chlorine
-16-
~L~t~
62301-1351
bleaches are typified by sodium hypochlorite (NaOC1), potassium
dichloroisocyanurate (59% available chlorine), and trichloro-
isocyanur acid (85% availabe chlorine). Oxyyen bleaches are re-
presented by sodium and potassium perborates, percarbonates, and
perphosphate and potassium monopersulfate. The oxygen bleaches
are preferred and the perborates, particularly sodium perborate
monohydrate is especially preferred.
The peroxygen compound is preferably used in admixture
with an activator therefor. Sui-table activators are those dis-
closed in U.S. Patent 4,264,466 or in column 1 of U.S. Patent
~,430,224. Polyacylated compounds are preferred activators among
these, compounds such as tetraacetyl ethylene diamine ("TAED")
and pentaacetyl glucose are particularly preferred.
The activiator usually interacts with the peroxygencompound to form a peroxyacid bleaching agent in the wash water.
It is preferred to include a sequestering agent of high complex-
ing power to inhibit any undesired reaction between such peroxy-
acid and hydrogen peroxide in the wash solution in the presence
of metal ions. Preferred sequestering agents are able to form
a complex with Cu2+ ions, such that the stability constant (pX)
of the complexation is equal to or greater than 6, at 25C, in
water, of an ionic strength of 0.1 mole/liter, pK being conven-
tionally defined by the formula: pK=-log K where K represents
the equilibrium constant. Thus, for example, the pK values for
complexation of copper ion w~th NTA and EDTA a-t the stated con-
ditions are 12.7 and 18.8, respectively. Suitable sequestering
agents include for example, in addition to those mentioned above,
diethylene triamine pentaacetic acid (DETPA); diethylene tri-
amine pentamethylene phosphonic acid (DTPMP); and ethylene di-
amine tetramethylene phosphonic acid (EDITEMPA).
-17-
s~
62301-1351
The composition may also contain an inorganic in-
soluble thickening agent or dispersant of very high sur~ace
area such as finely divided silica of extremely fine particle
size (e.g. of 5-100 millimicrons diameters such as sold under
the name Aerosil) or the o-ther highly voluminous inorganic
carrier materials disclosed in ~.S. Patent 3,630,929, in pro-
portions of 0.1-~0%, e.g. 1 to 5%. It is preferable, however,
that compositions which ~orm peroxyacids in the wash bath (e,g.
compositions con-taining peroxygen compound and activator there-
for) be substantially free of such compounds and of other sili-
cates; it has been found, for instance, that silica and sili-
cates promote the undesired decomposition of the peroxyacid.
In a preferred form of the invention, the mixture of
liquid non-ionic surfactant and solid inyredients is subjected
to an attrition type of mill in which the particle si~es of the
solid ingredients are reduced to less than about 10 microns,
e.g. to an average particle size of 2 to 10 microns or even
lower (e.g. 1 micron). Compositions whose dispersed partic]es
are of such small si~e have improved stability against separa-
tion or settling on storage.
In the grinding operation, it is preferred that theproportion of solid ingredients be high enough (e.g. at least
about 40% .such as about 50~) that the solid particles are in
contact with each other and are not substantially shielded from
one another by the non-ionic surfactant liquid. Mills which
employ grinding balls (ball mills) or similar mobile grinding
elements have given very good results. Thus, one may use a
laboratory batch attritor having 8 mm diameter steatite grind-
ing balls. For larger scale work a continuously operating mill
in which there are 1 mm or 1.5 mm diameter grinding balls work-
- 18 -
,~.
62301-1351
ing in a very small gap between a stator and a rotor operating
at a relatively high speed (e.g. a CoBall mi:Ll) may be
employed; when using such a mill, it is desirable to pass the
blend of non-ionic surfac-tant and solids first through a mil.l
which does not effect such fine grinding (e.g. a colloid mill)
to reduce the particle size to less than 100 microns (e.g., to
about 40~ microns) prior to the step of grinding to an average
particle diameter below about 10 microns in the continuous ball
mill.
The detergent compositions may be also advantageously
include a viscosity-controlling and gel-inhibiting agent in
order to lower the temperature at which the non-ionic surfac~
tant will for-m a gel when added to water. Such viscosity-
controlling and gel-inhibiting agents may be, for example,
lower alkanol, e.g~ ethyl alcohol (see U.S. Patent 3,953,3~0),
alkali metal formates and adipates (see U.S. Patent 4,368,147),
hexylene glycol, polyethylene glycol, and others. However, an
especially preferred class of viscosity-controlling and gel-
inhibiting compounds which can be used in the liquid non-ionic
detergent compositions of this~inven-tion are alkylene glycol
ether compounds represented by the following general formula
R'~
Ro(cHcH2o)nH
where R is a C1 Cs, preferably C2 to Cs, especially pre-
ferabl.y C2 to C4, and particularly C4 alkyl group,
R' is H or CH3, preferably H, and n is a number of from
about 1 to 4, pre~erably 2 to 4 on average.
Preferred examples of these gel-inhibiting compounds include
ethylene glycol monoethyl ether (C2Hs-0-CH2CH20H); and di-
ethylene glycol monobutyl ether (C4Hg-0-(CH2CH20)2H). Di-
- 19 -
' ` ','.' '`; ~ ` ` ~ .:
~ 2301-1351
ethylene glycol monoethyl ether is especially preferred because
it is uniquely e-ffective t.o control viscosity.
The use oE these ~lyco]. ether viscos;.ty control and
gel-inhi.bi-ting agents in substantially non-aqueous built liquid
non-ionic detergent compositions is disclosed in the copending,
commonly assigned Canadian Patent application No. 498,815
titled "LIQUID LA~NDRY DET~RGENT COMPOSITIO~ AND METHOD OF USE"
which was ~iled on 31 December 1985.
~ hile the preferred gel-inhihiting compounds,
particularly diethylene glycol monobutyl ether, can be the only
viscosity control and gel-inhibiting additive in the invention
compositions further improvements in the rheological properties
of the anhydrous ].iquid non-ionic surfac-tant compositions can
be obtained by including in the composition a small amount of a
non-ionic surEactant which has been modified to convert a free
hydroxyl group thereoE to a moiety having a free carboxyl
group, as discJ.osed in the aforementioned commonly assigned,
copending Canadian application No. 478,379 filed on April 4,
198~ such as a partial ester of a non-ionic surfactant and a
polycarboxylic acid and/or an acidic organic phosphorus
compound having an acidic - POH group, such as a partial ester
of phosphorous acid and an alkanol.
The free carboxyl group modified non-ionic surfac-
tants, which may be the same as, or differen-t from component
(B), and which may be broadly characterized as polyether
carboxylic acids, function to lower the tempera-ture at which
-the liquid non-ionic forms a gel with water, The acidic poly-
ether compound can also decrease the yield s-tress of such dis-
persions, aiding in -their dispensibility, without a correspond-
ing decrease in their stability against settling. Suitable
- 20 -
~'
62301-1351
polyether carboxylic acids contain a grouping of the formula
(OCH2 CH2-~p-~OÇH CH2-~q-Y-Z-COOH where R2 is hydrogen or methyl,
Y is oxygen or sulfur, Z is an organic linkagel p is a positive
number of from about 3 to about 50 and q is zero or a positive
number of up to 10. Specific examples include the half-ester
of Plurafac RA3Q with succinic anhydride, the half ester of
Dobanol 25-7 wlth succinic anhydride, the half es-ter of Dobanol
91-5 wi-th succinic anhydride, etc. Instead of a succinic acid
anhydride, other polycarboxylic acids or anhydrides may be
usedl e.g. maleic acidl maleic anhydride, glutaric acid, malo-
nic acidl succinic acid, phthalic acidl phthalic anhydride
citric acidl etc. Furthermorel other linkages may be used
such as etherl thioether or urethane linkagesl ~ormed by
conventional reactions. For instancel to form an ether link-
agel the non-ionic surfactant may be treated with a strong base
(to convert its OH group to an ONa group for instance) and then
reacted with a halocarboxylic acid such as chloroacetic acid or
chloropropionic acid or the corresponding bromo compound.
Thusl the resulting carboxylic acid may have the ~ormula
R-Y-ZCOOH where R is the residue of a non-ionic surfactan-t (on
removal of a terminal OH), Y
- 21 -
.
-22- 62301-1351
8~L
is oxygen or sulfur and Z represents an oryanic linkage such as
a hydrocarbon group of, say, one to ten carbon a-toms which may
be attached to the oxygen (or sulfur) of the formula directly or
by means of an in-tervening linkage such as an oxyyencontaining
O O
linkage, e.g. a " or " , etc.
-C- -C-NH-
The polyether carboxylic acid may be produced from a
polyether which is not a nonionic surfactant, e.g. it may be
made by reaction with a polyalkoxy compound such as polyethylene
glycol or a monoester or monoether thereof which does not have
-~he long alkyl chain characteristic of the nonionic surfactants.
Thus, R may have the formula lR2 where R is
Rl(OCH-CH ) -
hydrogen or methyl, Rl is alkylphenyl or alkyl or other chain
terminating group and "n" is a-t least 3 such as S to 25. When
the alkyl of R is a higher alkyl, R is a residue of a non-
ionic surfactant. As indicated above Rl may instead be hydrogen
or lower alkyl (e.g. methyl, ethyl, propyl, butyl) or lower
acyl (e.g. acetyl, etc.). The acidic polyether compound if
present in the detergent composition, is preferably added dis-
solved in the nonionic surfactant.
When the component (B) is used in a molar excess of
the component (C) cationic surfactant, the excess acid-
terminated nonionic may function as a gel-inhibiting agent.
As disclosed in the commonly assigned copending
Canadian application No. 478,380, filed April 4, 1985, the acidic
oryanic phosphorus compound having an acidic - POH group can
increase the stability of the suspension of builder, especially
polyphosphate builders, in the nonaqueous liquid nonionic sur-
factant.
The acidic organic phosphorus compound may be, for
instance, a partial ester of phosphoric acid and an alcohol such
as an alkanol which has a lipophilic character, having,
~ ~ ~ 62301-1351
for instance, more -than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
A specific example is a partial ester of phosphoric acid and
a C16 to C18 alkanol (Empiphos 5632 :from Marchon); it is made
up oE about 35~ monoester and 65% diester.
The inclusion of qui-te small amounts of the acidic organic
phosphorus compound makes the suspension significantly more
stable against settling on standing but remains pourable,
presumably, as a result of increasing the yield value oE the
suspension, but decreases its plastic viscosity. It is believed .
that the use of the acidic phosphorus compound may result in the
formation of a high energy physical bond between the -POH portion
of the molecule and the surfaces of the inorganic polyphosphate
builder so that these surfaces take on an organic character and
become more compatible with the non-ionicsurfactant~
The acidic organic phosphorous compound may be selected
from a wide variety of materials, in addition to the partial
esters of phosphoric acid and alkanols mentioned above. Thus,
one may employ a partial ester of phosphoric or phosphorous
acid with a mono or polyhydric alcohol such as hexylene glycol,
ethylene glycol, di- or tri-ethylene glycol or higher polyethy.~-
ene glycol, polypropylene glycol, glycerol, sorbitol, mono or
diglycerides of fatty acids, etc. in which one, two or more of
the alcoholic O~l groups of the molecule may be esterified with
the phosphorus acid. The alcohol may be a non-ionicsurfactant
such as an ethoxylated or ethoxylatedpropoxyl.atedhigher alkanol,
higher alkyl phenol, or higher alkyl amide. The -POH group need
not be bonded to the organic portion of the molecule through an
ester linkage; instead it may be directly bonded to carbon (as
in a phosphonic acid, such as a polystyrene in which some of the
aromatic rings carry phosphonic acid or phosphinic acid groups;
or an alkylphosphonic acid, such as propyl or laurylphosphonic
acid) or may be connected to the carbon through other intervening
23
~ 2301-1351
linkage (such as linkages through O, S or N atoms). Preferably,
-the carbon: phosphorus atomic ratio in the organic phosphorus
compound is at least about 3:1, such as 5-1, 10:1, 20:1, 30:1
or 40:1.
The liquid mixed surfactant compositions preferably include
therein at least one detergent builder suspended in the liquid
non-ionic surfactant. Suitable ranges of the surfactant and
builder components include from about 0.5 to 1 part by weight
of (A) non-ionic liquid surfactant; from about 0.12 to 5 parts
by weight of (B) acid-terminated non-ionic surfactant plus (C)
cationic surfactant at a weight ratio of (B) to (C) in the
range of from about 3:1 to 1:3l and from about 0.8 to 3 parts
by weight of said at least one detergent builder salt, prefer-
abliy at least one inorganic detergent builder salt, especially
preferably alkali metal polyphosphate, e.g. sodium tripolyphos-
phate.
Furthermore, as described above one or more additional
detergent adjuvants or additives can be included in the formula-
tion to provide specific functions commonly associated with
heavy duty laundry detergents~ Bleaching agents, for example,
are preferred additives. Optical brighteners, dyes, perfu~les,
enzymes, chelating agents, etc., are also commonly used and
highly beneficial additives.
In the preferred heavy duty liquid detergent compositions
of the invention, typical proportions (based on the total
composition, unless otherwise specified) of the ingredients
are as follows:
(A) liquid non-ionic surfactant - from about 20 to
80%, preferably about 30 to 70%, especially preferably about
40 to 60%;
(B) acid-terminated non-ionic surfactant from about
10 to 40%, preferably about 15 to 35%, especially preferably
24
~ ~ ~ 62301-1351
about 20 to 30%;
(C) cationic surfac-tant ~ from about 10 to 40%, preferably from
abou-t 15 to 35%, especially pre~erably about 20 -to 30%;
the sum of (A) + (B) ~ (C) being from about 30 to 100%
by weight of the total composition, preferably from about 40
to 90% by weight of the total composi-tion;
(D) detergent builder(s) - up to about 60%, preferably
within the range of about 10 to 60%, such as abou-t 20 to 50% r
especially about 25 to 40%;
(E) viscosity-controlling and gel-inhibiting agent(s):
(i) alkylene glycol ethers up to about 20%, for example from
about 2 to 15%;(ii) polyether carboxylic acid gel-inhibiting
compound up to about 10%, for example about 1 to 10%, prefer-
ably about 2 to 8%, (iii) others, e.g. lower (Cl-C4) alkanols,
glycols, etc. - up to ahout 10%, preferably up to about 5%,
for example 0.5 to 2%;
(F) acidic organic phosphoric acid compound, as anti-
set-tling agent: up to 5%, for example, in the range of 0.01
to 5%, such as about 0.05 to 2%, preferably about 0.1 to 1%.
Suitable ranges of other optional detergent additives
are: enzymes - 0 to 2%, especlally 0.7 to 1.3%; corrosion
inhibitors - about 0 to 40%, and preferably 5 to 30%;
anti~foam agents and suds-suppressors - 0 to 15%, preferably
0 to 5%, for example 0.1 to 3%;thickening agent and dispersants
- 0 to 15%, for example 0.1 to 10%, preferably 1 to 5%; soil
suspending or anti redeposition agents and anti-yellowing
agents-0 to 10%, preferably 0.5 to 5%; colorants, perfumes,
brighteners and bluing agents total weight 0% to about 2% and
preferably 0% to about 1%; pH modifiers and pH buffers - 0 to
5%, preferably 0 to 2%; bleaching agent - 0% to about 40% and
preferably 0% to about 25%, for example 2 to 20%; bleach
stabilizers and bleach activators 0 to about 15%, preferably
.f`
62301-1351
0 to 10%, for example, 0.1 to 8~; sequestering agent of high
complexiny power, in the range of up to about 5-~, preferably
about 1/~ to 3~, such as about 1/2 to 2~. In the selections o~
the adjuvants, they will be chosen to be compatible with the
main constituents of the detergent composition.
All proportions and percentages are by weight unless
otherwise indicated.
It is understood that the foregoing detailed description
is given merely by way of illustration and the variations may
be made therein without departing from the spirit of the
invention.
The preferred liquid non-ionic detergent compositions of
this invention are substantially anhydrous, although minor
amounts of water, e.g. up to about 5%, preferably up to about
2~, especially less than 1%, can be tolerated.
The mi~ed acid-terminated non-ionic/cationic surfactant
complex of this invention is also useful in aqueous cleaning
compositions as well as in powder detergent compositions for
its enhanced cleaning performance, especially in laundry
detergent compositions. The detergent mixture may be used in
place of part or all of the conventional detergent surfactant
component of the usual aqueous or powder detergent compositions.
In order to demonstrate the improved detergency, i.e.
cleaning performance, achieved by using both of the acid-
terminated non-ionic surfactant and the cationic surfactant, as
the compared to the effects achieved using only one of these
two surfactants~ the following tests were performed:
A liquid non-ionic surfactant composition was prepared
with the following ingredients:
26
62301-1351
Amount (grams)
Surfactan-t T7 0.375
Surfaetan-t T9 0.375
Sodium tripolyphosphate 1.5
Mixture of: 0.25
Acid terminated non-ionie
Cationic Surfactant
The acid terminated non-ionie was aeid--terminated Dobanol
91-5 prepared in Example C.
The cationie surfaetant was Ethoquat 2T14 which is avail-
able from Armak Chemieal Co.
The ratio of the aeid-terminated non-ionic and cationic
surfactants in the 0.25 gram mixture was varied as follows
ljO, 3:1, 1:1, 1:3 and 0:1~ Each of the resulting five formula-
tions was added to a bowl containing 600 ml -tapwater at 40C
or 60C. In eaeh solution, 6 Krefield soiled swa-tehes were
eleaned. The ~Rd values were measured. The results are
shown in the following table:
Ratio aeid-terminated non-ionic ~Rd
cationic in 0 25 gram mixture 40C 60C
1:0 8.1 16.0
3:1 9.3 16.5
1:1 11.4 18.3
1:3 11.9 18.0
0:1 10.4 12.2
These results elearly demonstrate the improved cleaning
preformance of the mixture of acid-terminated non-ionic
surfactant with the cationic surfactant, especially at the
1:1 mixing ratios.
27
